Methods and apparatus for predicting glass dynamics

ABSTRACT

Computer-implemented methods and apparatus are provided for predicting/estimating (i) a non-equilibrium viscosity for at least one given time point in a given temperature profile for a given glass composition, (ii) at least one temperature profile that will provide a given non-equilibrium viscosity for a given glass composition, or (iii) at least one glass composition that will provide a given non-equilibrium viscosity for a given time point in a given temperature profile. The methods and apparatus can be used to predict/estimate stress relaxation in a glass article during forming as well as compaction, stress relaxation, and/or thermal sag or thermal creep of a glass article when the article is subjected to one or more post-forming thermal treatments.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation of U.S. patent application Ser. No. 13/662,652,filed on Oct. 29, 2012, which claims the benefit of priority under 35U.S.C. §119 of U.S. Provisional Application Ser. No. 61/553,459, filedon Oct. 31, 2011, the contents of which are relied upon and incorporatedherein by reference in their entireties.

FIELD

This disclosure relates to methods and apparatus forpredicting/estimating the non-equilibrium viscosity of glasses and/orglass-forming liquids (hereinafter referred to as “glass materials” orsimply “materials”).

DEFINITIONS AND CONVENTIONS

The terms “viscosity,” “equilibrium viscosity,” and “non-equilibriumviscosity” refer to shear viscosity, i.e., the response of the glass toan applied shear stress.

All viscosities referred to herein are assumed to have been divided bytheir units, e.g., Pa-s, to make numbers upon which the log function canoperate.

As used herein, the glass transition temperature (T_(g)(x)) of amaterial is the temperature at which it has an equilibrium viscosity of10¹² Pa-s.

The term “glass article” is used in its broadest sense to include anyobject made wholly or partly of glass and/or a glass ceramic.

BACKGROUND

The problem of predicting the properties of glass materials has been alongstanding one in the field of glass and glass-ceramic chemistry.Because most glasses and glass-ceramics (referred to collectively hereinas “glasses”) contain a relatively large number of components, e.g.,three to six or more in many cases, the compositional space ismulti-dimensional, making experimental study of the entire spaceeconomically impractical. Yet, from melting through to forming, theproduction of glass articles would clearly benefit from an ability topredict/estimate glass properties based on glass composition or,conversely, to select glass compositions based on desired properties.Likewise, the ability to predict/estimate the behavior of glass articlesduring use, e.g., during post-forming thermal processing, would be ofgreat value to the art.

Among all the technologically useful properties of a glass-formingsystem, the viscosity of the melt is undoubtedly among the mostimportant. Every stage of industrial glass production—from the initialmelting, mixing, and fining to the final forming operations—requirescareful control of viscosity. For example, viscosity controls the ratesof melting and of fining in a glass melting tank. Similarly, each glassforming operation, e.g., fiber forming or the final annealing ofcontainer glass, requires a certain well-defined viscosity range andconsequently a specific temperature range for that operation. See, forexample, Varshneya A K (2006) Fundamentals of Inorganic Glasses, 2nd ed.(Society of Glass Technology, Sheffield, UK).

Non-equilibrium viscosity is particularly important with regard topost-forming processing of glass articles. Specifically, non-equilibriumviscosity determines the relaxation rate of a final glass article (finalglass product). As just one example, non-equilibrium viscosity controlsthe compaction behavior of display glasses (e.g., the glass sheets usedas substrates in the production of liquid crystal displays) duringcustomer heat treatment cycles. It should thus come as no surprise thatthe details of the viscosity-temperature-time relationship play acritical role in researching new glass compositions for display andother applications.

Among other reasons, the problem of relating equilibrium viscosity totemperature and composition is challenging because from the initialglass melting to final forming, viscosity varies by over twelve ordersof magnitude. See, for example, Varshneya (2006), supra. Equilibriumviscosity is also sensitive to small changes in composition, especiallyin silicate melts where small levels of impurities can have a profoundinfluence on the flow behavior. It is thus of great importance to haveaccurate knowledge of the scaling of viscosity with both composition (x)and temperature (T). Unfortunately, measurement of η_(eq)(T,x) ischallenging for high temperature melts, and low temperature measurements(i.e., in the high viscosity range, 10¹⁰ to 10¹⁵ Pa-s) are timeconsuming and often prohibitively expensive. See, for example, Varshneya(2006), supra. For non-equilibrium viscosities, the situation is evenmore complex because in addition to depending on composition (x) andcurrent temperature (T), the non-equilibrium viscosity of a glassarticle also depends on the glass's thermal history, in particular, itsthermal history from that point in time when it was last in thermalequilibrium with its surroundings.

In view of this state of the art, a need exists for more effectivemethods and apparatus for predicting/estimating the properties of glassmaterials and, in particular, for predicting/estimating the dependenceof viscosity, specifically, non-equilibrium viscosity, on temperature,thermal history, and/or composition. The present disclosure addressesthese problems.

SUMMARY

In accordance with a first aspect, a method is disclosed for making aglass article which includes:

-   -   (I) melting batch materials to produce molten glass (e.g.,        melting batch materials using commercial, laboratory,        experimental, or other glass making equipment now known or        subsequently developed); and    -   (II) forming a glass article from the molten glass (e.g.,        forming a glass article using commercial, laboratory,        experimental, or other glass making equipment now known or        subsequently developed);    -   wherein:        -   (A) the batch materials include a plurality of            viscosity-affecting components which become at least part of            the glass of the glass article (i.e., the            viscosity-affecting components can make up the entire glass            composition or only a part of the glass composition); and        -   (B) the method is characterized by the viscosity-affecting            components and/or their concentrations being at least            partially based on a computer-implemented model which            relates glass viscosity as a function of time to glass            composition.

In accordance with a second aspect, a computer-implemented method isdisclosed for:

-   -   (i) predicting/estimating a non-equilibrium viscosity for at        least one given time point in a given temperature profile for a        given glass composition, the given temperature profile beginning        with a time point at which the given glass composition is at        equilibrium at a given temperature; or    -   (ii) predicting/estimating at least one temperature profile that        will provide a given non-equilibrium viscosity for a given glass        composition, the temperature profile beginning with a time point        at which the given glass composition is at equilibrium at a        given temperature; or    -   (iii) predicting/estimating at least one glass composition that        will provide a given non-equilibrium viscosity for a given time        point in a given temperature profile, the given temperature        profile beginning with a time point at which the glass        composition is at equilibrium at a given temperature;    -   the method including using a computer to evaluate at a series of        time points an equation that relates non-equilibrium viscosity η        to glass composition x, temperature T, and fictive temperature        T_(f), where x={x₁, x₂, . . . x_(i) . . . x_(N)} are        concentrations of the glass's viscosity-affecting components,        and T and T_(f) are functions of time.

Apparatus for practicing the above methods, specifically, programmedcomputers and non-transitory computer readable storage media, is alsodisclosed.

With regard to the viscosity-affecting components of a glasscomposition, it should be noted that those components can includeclusters of constituents and/or constituents that might in some contextsbe considered contaminants, e.g., water which would be considered acontaminant in, for example, glasses used in optical waveguide fibers.In many cases, the basic constituents of the glass will be oxides, itbeing understood that the technology disclosed herein can also be usedwith non-oxide glasses if desired. As to units, the composition can beexpressed in any convenient units, mole percent and weight percent beingthe most common choices.

The above summaries of the various aspects of the disclosure are onlyfor the convenience of the reader and are not intended to and should notbe interpreted as limiting the scope of the invention. More generally,it is to be understood that both the foregoing general description andthe following detailed description are merely exemplary of the inventionand are intended to provide an overview or framework for understandingthe nature and character of the invention.

Additional features and advantages of the invention are set forth in thedetailed description which follows, and in part will be readily apparentto those skilled in the art from that description or recognized bypracticing the invention as exemplified by the description herein. Theaccompanying drawings are included to provide a further understanding ofthe invention, and are incorporated in and constitute a part of thisspecification. It is to be understood that the various features of theinvention disclosed in this specification and in the drawings can beused in any and all combinations.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot comparing deflection versus time data from beam bendingexperiments (solid curves) with predicted results obtained using anembodiment of the non-equilibrium viscosity model disclosed herein(dashed curves). The glass used in the experiments and modeling wasGlass A of Example 1.

FIG. 2 is a plot of the viscosity behavior corresponding to thedeflection behavior of FIG. 1.

FIG. 3 is a plot comparing deflection versus time data from beam bendingexperiments (solid curves) with predicted results obtained using anembodiment of the non-equilibrium viscosity model disclosed herein(dashed curves). The glass used in the experiments and modeling wasGlass B of Example 1.

FIG. 4 is a plot of the viscosity behavior corresponding to thedeflection behavior of FIG. 3.

FIG. 5 is a non-limiting, representative plot of glass temperatureversus time, i.e., a non-limiting, representative temperature profile,for a glass ribbon produced by a fusion process.

FIG. 6 is a non-limiting, representative plot of glass temperatureversus time, i.e., a non-limiting, representative temperature profile,for a glass substrate during formation of an electronic component on thesubstrate.

FIG. 7 is a non-limiting, representative plot of glass temperatureversus time, i.e., a non-limiting, representative temperature profile,for a glass substrate during ion-exchange strengthening.

FIG. 8 is a non-limiting, representative plot of glass temperatureversus time, i.e., a non-limiting, representative temperature profile,for a glass substrate during formation of a photovoltaic device on thesubstrate.

DETAILED DESCRIPTION

Relaxation behavior is of critical importance for many glass products.For example, liquid crystal display glass is subjected to thermaltreatments during deposition of transistors on the glass substrate.Relaxation of the glass during these heat treatment cycles can lead tocompaction, i.e., a permanent change in the dimensions of the glass. Thequality of high purity fused silica depends on obtaining a uniformthermal history throughout the glass; any uneven relaxation effect willlead to a deterioration of the quality of the final product throughbirefringence and optical inhomogeneity. When glass sheets are used assubstrates and subjected to elevated temperature during processing,glass relaxation can cause thermal sag or creep. Low creep duringcustomer processes can be a key aspect enabling successful products. Inanother context, the amount of Rayleigh scattering exhibited by glassoptical fibers is controlled by density fluctuations in the glass, whichexhibit nonmonotonic relaxation behavior as the glass relaxes.

Thus, accurate predictions/estimates of glass relaxation is vital to allglass products. There are two important factors governing glassrelaxation: thermodynamics and kinetics. Thermodynamically, glass is anon-equilibrium system that would like to relax to the metastablesupercooled liquid state. This relaxation typically involves acontinuous change in the volume, enthalpy, and other properties of theglass as it approaches the liquid state. While the presence of athermodynamic driving force is a necessary condition for glassrelaxation, by itself it is insufficient since the glass must also haveenough thermal energy and/or time to enable the kinetics of relaxation.Assuming isobaric conditions, the kinetics of the glass depend on threefactors: composition, temperature, and thermal history. The importanceof thermal history cannot be overstated, since the dynamics of twoglasses of the same composition and at the same temperature can vary bymany orders of magnitude depending on the details of thermal history.

In accordance with the present disclosure, methods and apparatus areprovided for predicting/estimating the composition dependence of glassydynamics. The techniques described herein are based on enthalpylandscape and temperature-dependent constraint theories, a discussion ofwhich can be found in Mauro, et al., “Nonequilibrium Viscosity OfGlass,” Physical Review B, 2009, 80:094204, the content of which in itsentirety is incorporated herein by reference.

Example 1 set forth below illustrates the efficacy of the methodsdisclosed herein. This example uses display glass compositions, i.e.,glass compositions which during their normal use undergo post-formingthermal treatments, and thus the glassy dynamics of these compositionsare of particular relevance to purchasers of these glass articles. Theexample further illustrates the ability to use experimental data for oneglass (Glass A) to predict non-equilibrium viscosities of another glass(Glass B) without the need to make measurements of the non-equilibriumbehavior of the second glass. This is an important aspect of the presentdisclosure because, among other things, it allows glass scientists toidentify suitable glass compositions for particular applications withoutthe need to fully characterize the compositions' non-equilibriumbehavior by measuring that behavior for each new composition.

In an embodiment, the methods and apparatus for predicting/estimatingnon-equilibrium viscosity disclosed herein have as their base anequation of the form:

log₁₀η(T,T _(f) ,x)=y(T,T _(f) ,x)log₁₀η_(eq)(T _(f) ,x)+[1−y(T,T _(f),x)] log₁₀η_(ne)(T,T _(f) ,x)  (1)

In this equation, η is the glass's non-equilibrium viscosity which is afunction of composition through the variable “x”, η_(eq)(T_(f), x) is acomponent of η attributable to the equilibrium liquid viscosity of theglass evaluated at fictive temperature T_(f) for composition x(hereinafter referred to as the “first term of Eq.(1)”), η_(ne)(T,T_(f),x) is a component of η attributable to the non-equilibriumglassy-state viscosity of the glass at temperature T, fictivetemperature T_(f), and composition x (hereinafter referred to as the“second term of Eq.(1)”), and y is an ergodicity parameter whichsatisfies the relationship: 0≦y(T,T_(f),x)<1.

In an embodiment, y(T,T_(f),x) is of the form:

$\begin{matrix}{{y\left( {T,T_{f},x} \right)} = \left\lbrack \frac{\min \left( {T,T_{f}} \right)}{\max \left( {T,T_{f}} \right)} \right\rbrack^{{p{(x_{ref})}}{{m{(x)}}/{m{(x_{ref})}}}}} & (2)\end{matrix}$

(For convenience, the product p(x_(ref))m(x)/m(x_(ref)) will be referredto herein as “p(x)”.)

This formulation for y(T,T_(f),x) has the advantage that throughparameter values p(x_(ref)) and m(x_(ref)), Eq.(2) allows all the neededparameters to be determined for a reference glass composition x_(ref)and then extrapolated to new target compositions x. The parameter pcontrols the width of the transition between equilibrium andnon-equilibrium behavior in Eq.(1), i.e., when the value of y(T,T_(f),x)calculated from Eq.(2) is used in Eq.(1). p(x_(ref)) is the value of pdetermined for the reference glass, e.g., Glass A of Example 1, byfitting to experimentally measured data that relates to relaxation,e.g., by fitting to beam bending data and/or compaction data. Theparameter m relates to the “fragility” of the glass, with m(x) being forcomposition x and m(x_(ref)) being for the reference glass. Theparameter m is discussed further below.

In an embodiment, the first term of Eq.(1) is of the form:

$\begin{matrix}{{\log_{10}{\eta_{eq}\left( {T_{f},x} \right)}} = {{\log_{10}\eta_{\infty}} + {\left( {12 - {\log_{10}\eta_{\infty}}} \right){\frac{T_{g}(x)}{T_{f}} \cdot {\exp \left\lbrack {\left( {\frac{m(x)}{12 - {\log_{10}\eta_{\infty}}} - 1} \right)\left( {\frac{T_{g}(x)}{T_{f}} - 1} \right)} \right\rbrack}}}}} & (3)\end{matrix}$

In this equation, η_(∞)=10^(−2.9) Pa·s is the infinite-temperature limitof liquid viscosity, a universal constant, T_(g)(x) is the glasstransition temperature for composition x, and, as discussed above, m(x)is the fragility for composition x, defined by:

$\begin{matrix}{{{m(x)} = \frac{{\partial\log_{10}}{\eta_{eq}\left( {T,x} \right)}}{\partial\left( {{T_{g}(x)}/T} \right)}}}_{T = {T_{g}{(x)}}} & (4)\end{matrix}$

Both the glass transition temperature for composition x and thecomposition's fragility can be expressed as expansions which employempirically-determined fitting coefficients. Such expansions arediscussed in detail in co-pending, commonly-assigned U.S. patentapplication Ser. No. 12/896,355, entitled “METHODS AND APPARATUS FORPREDICTING GLASS PROPERTIES,” which was filed on Oct. 1, 2010, thecontent of which in its entirety is hereby incorporated herein byreference.

As discussed in the above application, the glass transition temperatureexpansion can be derived from constraint theory, which makes theexpansion inherently nonlinear in nature. The fragility expansion can bewritten in terms of a superposition of contributions to heat capacitycurves, a physically realistic scenario. The net result of the choice ofthese expansions is that Eq. (3) can accurately cover a wide range oftemperatures (i.e., a wide range of viscosities) and a wide range ofcompositions.

As a specific example of a constraint theory expansion of glasstransition temperature, the composition dependence of T_(g) can, forexample, be given by an equation of the form:

$\begin{matrix}{{{T_{g}(x)} = \frac{K_{ref}}{{- {\sum_{i}{x_{i}{n_{i}/{\sum_{i}{x_{j}N_{j}}}}}}}}},} & (5)\end{matrix}$

where the n_(i)'s are fitting coefficients, d is the dimensionality ofspace (normally, d=3), the N_(j)'s are the numbers of atoms in theviscosity-affecting components of the glass (e.g., N=3 for SiO₂, N=5 forAl₂O₃, and N=2 for CaO), and K_(ref) is a scaling parameter for thereference material x_(ref), the scaling parameter being given by:

$\begin{matrix}{{K_{ref} = {{T_{g}\left( x_{ref} \right)}\left( {{- \frac{\sum_{i}{x_{{ref},i}n_{i}}}{\sum_{j}{x_{{ref},j}N_{j}}}}} \right)}},} & (6)\end{matrix}$

where T_(g)(x_(ref)) is a glass transition temperature for the referencematerial obtained from at least one viscosity measurement for thatmaterial.

The summations in Eqs. (5) and (6) are over each viscosity-affectingcomponent i and j of the material, the x_(i)'s can, for example, beexpressed as mole fractions, and the n_(i)'s can, for example, beinterpreted as the number of rigid constraints contributed by thevarious viscosity-affecting components. In Eqs. (5) and (6), thespecific values of the n_(i)'s are left as empirical fitting parameters(fitting coefficients). Hence, in the calculation of T_(g)(x) there isone fitting parameter for each viscosity-affecting component i.

As a specific example of a fragility expansion based on a superpositionof heat capacity curves, the composition dependence of m can, forexample, be given by an equation of the form:

$\begin{matrix}{{{{m(x)}/m_{0}} = \left( {1 + {\sum\limits_{i}{x_{i}\frac{\Delta \; C_{p,i}}{\Delta \; S_{i}}}}} \right)},} & (7)\end{matrix}$

where m₀=12−log₁₀η_(∞), the ΔC_(p,i)'s are changes in heat capacity atthe glass transition, and the ΔS_(i)'s are entropy losses due to ergodicbreakdown at the glass transition. The constant m₀ can be interpreted asthe fragility of a strong liquid (a universal constant) and isapproximately equal to 14.9.

The values of ΔC_(p,i)/ΔS_(i) in Eq. (7) are empirical fittingparameters (fitting coefficients) for each viscosity-affecting componenti. Hence, the complete equilibrium viscosity model of Eq. (3) caninvolve only two fitting parameters per viscosity-affecting component,i.e., n_(i) and ΔC_(p,i)/ΔS_(i). Techniques for determining values forthese fitting parameters are discussed in the above-referencedco-pending U.S. application incorporated herein by reference.

Briefly, in one embodiment, the fitting coefficients can be determinedas follows. First, a set of reference glasses is chosen which spans atleast part of a compositional space of interest, and equilibriumviscosity values are measured at a set of temperature points. An initialset of fitting coefficients is chosen and those coefficients are usedin, for example, an equilibrium viscosity equation of the form of Eq.(3) to calculate viscosities for all the temperatures and compositionstested. An error is calculated by using, for example, the sum of squaresof the deviations of log(viscosity) between calculated and measuredvalues for all the test temperatures and all the reference compositions.The fitting coefficients are then iteratively adjusted in a directionthat reduces the calculated error using one or more numerical computeralgorithms known in the art, such as the Levenburg-Marquardt algorithm,until the error is adequately small or cannot be further improved. Ifdesired, the process can include checks to see if the error has become“stuck” in a local minimum and, if so, a new initial choice of fittingcoefficients can be made and the process repeated to see if a bettersolution (better set of fitting coefficients) is obtained.

When a fitting coefficient approach is used to calculate T_(g)(x) andm(x), the first term of Eq. (1) can be written more generally as:

log₁₀η_(eq)(T _(f) ,x)=C ₁ +C ₂·(f ₁(x,FC1)/T _(f))·exp([f₂(x,FC2)−1]·[f ₁(x,FC1)/T _(f)−1])

where:

-   -   (i) C₁ and C₂ are constants,    -   (ii) FC1={FC¹ ₁,FC¹ ₂ . . . FC¹ _(i) . . . FC¹ _(N)} is a first        set of empirical, temperature-independent fitting coefficients,        and    -   (iii) FC2={FC² ₁,FC² ₂ . . . FC² _(i) . . . FC² _(N)} is a        second set of empirical, temperature-independent fitting        coefficients.

Returning to Eq. (1), in an embodiment, the second term of Eq.(1) is ofthe form:

$\begin{matrix}{{\log_{10}{\eta_{ne}\left( {T,T_{f},x} \right)}} = {{A\left( x_{ref} \right)} + \frac{\Delta \; {H\left( x_{ref} \right)}}{{kT}\; \ln \; 10} - {\frac{S_{\infty}(x)}{k\; \ln \; 10}{\exp \left\lbrack {{- \frac{T_{g}(x)}{T_{f}}}\left( {\frac{m(x)}{12 - {\log_{10}\eta_{\infty}}} - 1} \right)} \right\rbrack}}}} & (8)\end{matrix}$

As can be seen, like Eq. (3), this equation depends on T_(g)(x) andm(x), and those values can be determined in the same manner as discussedabove in connection with Eq. (3). A and ΔH could in principle becomposition dependent, but in practice, it has been found that they canbe treated as constants over any particular range of compositions ofinterest. Hence the full composition dependence of η_(ne)(T,T_(f),x) iscontained in the last term of the above equation. The infinitetemperature configurational entropy component of that last term, i.e.,S_(∞)(x), varies exponentially with fragility. Specifically, it can bewritten as:

$\begin{matrix}{{S_{\infty}(x)} = {{S_{\infty}\left( x_{ref} \right)}{\exp \left( \frac{{m(x)} - {m\left( x_{ref} \right)}}{12 - {\log_{10}\eta_{\infty}}} \right)}}} & (9)\end{matrix}$

As with p(x_(ref)) discussed above, the value of S_(∞)(x_(ref)) for thereference glass can be obtained by fitting to experimentally measureddata that relates to relaxation, e.g., by fitting to beam bending dataand/or compaction data.

When a fitting coefficient approach is used to calculate T_(g)(x) andm(x), the second term of Eq. (1) can be written more generally as:

log₁₀η_(ne)(T,T _(f) ,x)=C ₃ +C ₄ /T−C ₅·exp(f ₂(x,FC2)−C ₆)·exp([f₂(x,FC2)−1]·[f ₁(x,FC1)/T _(f)])

where:

-   -   (i) C₃, C₄, C₅, and C₆ are constants,    -   (ii) FC1={FC¹ ₁FC¹ ₂ . . . FC¹ _(i) . . . FC¹ _(N)} is a first        set of empirical, temperature-independent fitting coefficients,        and    -   (iii) FC2={FC² ₁,FC² ₂ . . . FC² _(i) . . . FC² _(N)} is a        second set of empirical, temperature-independent fitting        coefficients.

When a fitting coefficient approach is used to calculate T_(g)(x) andm(x) for both the first and second terms of Eq. (1), those terms can bewritten more generally as:

log₁₀η_(eq)(T _(f) ,x)=C ₁ +C ₂·(f ₁(x,FC1)/T _(f))·exp([f₂(x,FC2)−1]·[f ₁(x,FC1)/T _(f)−1]),

and

log₁₀η_(ne)(T,T _(f) ,x)=C ₃ +C ₄ /T−C ₅·exp(f ₂(x,FC2)−C ₆)·exp([f₂(x,FC2)−1]·[f ₁(x,FC1)/T _(f)]),

where:

-   -   (i) C₁, C₂, C₃, C₄, C₅, and C₆ are constants,    -   (ii) FC1={FC¹ ₁FC¹ ₂ . . . FC¹ _(i) . . . FC¹ _(N)} is a first        set of empirical, temperature-independent fitting coefficients,        and    -   (iii) FC2={FC² ₁FC² ₂ . . . FC² _(i) . . . FC² _(N)} is a second        set of empirical, temperature-independent fitting coefficients.

Although the use of glass transition temperature and fragility arepreferred approaches for developing expressions for f₁(x,FC1) andf₂(x,FC2) in the above expressions, other approaches can be used, ifdesired. For example, the strain point or the softening point of theglass, together with the slope of the viscosity curves at thesetemperatures can be used.

As can be seen from Eqs. (1), (2), (3), (8), and (9), thecomputer-implemented model disclosed herein for predicting/estimatingnon-equilibrium viscosity can be based entirely on changes in glasstransition temperature T_(g)(x) and fragility m(x) with composition x,which is an important advantage of the technique. As discussed above,T_(g)(x) and m(x) can be calculated using temperature dependentconstraint theory and a superposition of heat capacity curves,respectively, in combination with empirically-determined fittingcoefficients. Alternatively, T_(g)(x) and m(x) can be determinedexperimentally for any particular glass of interest, which is theapproach used in Example 1 below.

In addition to their dependence on T_(g)(x) and m(x), Eqs. (1), (2),(3), and (8) also depend on the glass's fictive temperature T_(f). Adiscussion of fictive temperature can be found in, for example, Mauro,et al., “Fictive Temperature and the Glassy State,” J. Am. Ceram. Soc.,2009, 92:75-86, the content of which in its entirety is incorporatedherein by reference. In accordance with the present disclosure, thecalculation of the fictive temperature associated with the thermalhistory and glass properties of a particular glass composition canfollow established methods, except for use of the non-equilibriumviscosity model disclosed herein to set the time scale associated withthe evolving T_(f). A non-limiting, exemplary procedure that can be usedis as follows.

In overview, the procedure uses an approach of the type known as“Narayanaswamy's model” (see, for example, Relaxation in Glass andComposites by George Scherer (Krieger, Fla., 1992), chapter 10), exceptthat the above expressions for non-equilibrium viscosity are usedinstead of Narayanaswamy's expressions (see Eq.(10.10) or Eq.(10.32) ofScherer).

A central feature of Narayanaswamy's model is the “relaxation function”which describes the time-dependent relaxation of a property from aninitial value to a final, equilibrium value. The relaxation functionM(t) is scaled to start at 1 and reach 0 at very long times. A typicalfunction used for this purpose is a stretched exponential, e.g.:

$\begin{matrix}{{M(t)} = {\exp \left( {- \left( \frac{t}{\tau} \right)^{b}} \right)}} & (10)\end{matrix}$

Other choices are possible, including:

$\begin{matrix}{M_{s} = {\sum\limits_{i = 1}^{N}{w_{i}{\exp \left( {{- \alpha_{i}}\frac{t}{\tau}} \right)}}}} & (11)\end{matrix}$

where the α_(i) are rates that represent processes from slow to fast andthe w_(i) are weights that satisfy:

$\begin{matrix}{{\sum\limits_{i = 1}^{N}w_{i}} = 1} & (12)\end{matrix}$

The two relaxation function expressions of Eqs. (10) and (11) can berelated by choosing the weights and rates to make M_(s) most closelyapproximate M, a process known as a Prony series approximation. Thisapproach greatly reduces the number of fitting parameters becausearbitrarily many weights and rates N can be used but all are determinedby the single stretched exponential constant b. The single stretchedexponential constant b is fit to experimental data. It is greater than 0and less than or equal to 1, where the value of 1 would cause therelaxation to revert back to single-exponential relaxation.Experimentally, the b value is found most often to lie in the range ofabout 0.4 to 0.7.

In Eqs. (10) and (11), t is time and τ is a time scale for relaxationalso known as the relaxation time. Relaxation time is stronglytemperature dependent and is taken from a “Maxwell relation” of theform:

τ(T,T _(f))=η(T,T _(f))/G(T,T _(f)).  (13)

In this expression, G(T, T_(f)) is a shear modulus although it need notbe a measured shear modulus. In an embodiment, G(T,T_(f)) is taken as afitting parameter that is physically approximately equal to a measuredshear modulus. η is the non-equilibrium viscosity of Eq. (1), whichdepends on both T and T_(f).

When relaxation proceeds during a time interval over which thetemperature is changing, then the time dependence of both thetemperature and the fictive temperature need to be taken into accountwhen solving for time-varying fictive temperature. Because fictivetemperature is involved in setting the rate of its own time dependencethrough Eq. (13), it shows up on both sides of the equation as shownbelow. Consistent with Eq. (11), it turns out that the overall fictivetemperature T_(f) can be represented as a weighted sum of “fictivetemperature components” or modes in the form

$\begin{matrix}{T_{f} = {\sum\limits_{i = 1}^{N}{w_{i}T_{fi}}}} & (14)\end{matrix}$

using the same weights as before, i.e., the same weights as in Eqs. (11)and (12). When this is done, the time evolution of fictive temperaturesatisfies a set of coupled differential equations, where each of T_(f),T_(fi), and T are a function of time:

$\begin{matrix}{{\frac{T_{fi}}{t} = {{\frac{\alpha_{i}}{\tau \left( {T,T_{f}} \right)}\left( {T - T_{fi}} \right)} = {\frac{{G\left( {T,T_{f}} \right)}\alpha_{i}}{\eta \left( {T,T_{f}} \right)}\left( {T - T_{fi}} \right)}}},\; {i = {1\mspace{11mu} \ldots \mspace{11mu} {N.}}}} & (15)\end{matrix}$

Note that the time evolution of fictive temperature components dependson the present value of the overall fictive temperature T_(f) throughthe role of setting the time scale of relaxation through the viscosity.In this approach, it is only the viscosity that couples together thebehavior of all the fictive temperature components. Recalling that therates α_(i) and the weights w_(i) are fixed by the single value of thestretching exponent b, they and G(T, T_(f)) can be taken to betime-independent, although other choices are possible. When numericallysolving the set of N equations of Eq. (15), the techniques used need totake into account both the fact that individual equations can havewildly different time scales and the manner in which T_(f) occurs on theright hand side inside the viscosity.

Once the fictive temperature components are known at any given timethrough Eq. (15), the fictive temperature itself is calculated using Eq.(14). In order to solve Eq. (15) by stepping forward in time it isnecessary to have initial values for all the fictive temperaturecomponents. This can be done either by knowing their values based onprevious calculations or else by knowing that all the fictivetemperature components are equal to the current temperature at aninstant of time.

Eventually all calculations must have started in this way at someearlier time, i.e., at some point in time, the glass material must be atequilibrium at which point all the fictive temperature components areequal to the temperature. Thus, all calculations must be traceable backto having started in equilibrium.

It should be noted that within this embodiment, all knowledge of thethermal history of the glass is encoded in the values of the fictivetemperature components (for a given set of the weights and so forth thatare not time-dependent). Two samples of the same glass that shareidentically the same fictive temperature components (again, assuming allother fixed model parameters are the same) have mathematically identicalthermal histories. This is not the case for two samples that have thesame overall T_(f), as that T_(f) can be the result of many differentweighted sums of different T_(fi)'s.

The mathematical procedures described above can be readily implementedusing a variety of computer equipment and a variety of programminglanguages or mathematical computation packages such as MATHEMATICA(Wolfram Research, Champaign, Ill.), MATLAB (MathWorks of Natick,Mass.), or the like. Customized software can also be used. Output fromthe procedures can be in electronic and/or hard copy form, and can bedisplayed in a variety of formats, including in tabular and graphicalform. For example, graphs of the types shown in the figures can beprepared using commercially available data presentation software such asMICROSOFT's EXCEL program or similar programs. Software embodiments ofthe procedures described herein can be stored and/or distributed in avariety of forms, e.g., on a hard drive, diskette, CD, flash drive, etc.The software can operate on various computing platforms, includingpersonal computers, workstations, mainframes, etc.

Without intending to limit it in any manner, the invention will befurther illustrated by the following examples. Among other things, theexamples illustrate representative applications of the technologydisclosed herein to glass making and glass processing.

It should, of course, be understood that these particular examples arenot limiting and the technology disclosed herein can be employed in avariety of ways to understand and/or to improve glass manufacturing andglass processing. Also, the technology can be used to discover new glasscompositions and/or to identify existing compositions that meet adesired set of viscosity criteria. For example, non-equilibriumviscosity predictions based on the present disclosure can be used toguide experimental composition research, to pre-screen candidate glassesso as to reduce the number of compositions that need to be melted,and/or to reduce the number of viscosity measurements that need to beperformed. Further applications for the technology disclosed herein willbe evident to skilled persons from the present disclosure.

Example 1

This example illustrates the ability of Eqs. (1), (2), (3), and (8) toaccurately predict/estimate the non-equilibrium viscosity of glassmaterials. In particular, this example uses beam bending experiments toestablish that the above expressions accurately reproducenon-equilibrium viscosity for a range of glass compositions,temperatures, and thermal histories (i.e. fictive temperatures).

The beam bending tests used a rectangular beam of the glass materialfrom which was hung a small weight. The beam was held at a fixedtemperature and its small viscous deformations over time were accuratelymeasured. The observed deflection and the underlying viscosity arerelated by

$\begin{matrix}{{{y(t)} = {C{\overset{t}{\int\limits_{0}}\; \frac{t^{\prime}}{\eta \left( {{T\left( t^{\prime} \right)},{T_{f}\left( t^{\prime} \right)}} \right)}}}}\;} & (16)\end{matrix}$

where y(t) is the deflection of the center of the beam at time t, η isthe non-equilibrium viscosity, and C is a standard beam-bendingviscometry constant that takes account of the load hanging from the beamand the beam's geometry and is given by:

$\begin{matrix}{C = {{\frac{{gL}^{3}}{120{wh}^{3}}\left\lbrack {M_{load} + \frac{\rho \; {whL}}{1.6}} \right\rbrack}.}} & (17)\end{matrix}$

In Eq. (17), g is the acceleration of gravity in cm/s², ρ is the densityof the glass bar in g/cm³, M_(load) is the total load mass in grams, Lis the span or distance between supports, and w is the width and h isthe (vertical) thickness of the beam. All of the lengths are measured incm, such that the resulting C is in units of Pa-cm.

Two glasses were used in the experiments, one of which (Glass A)contained six components, i.e., SiO₂, Al₂O₃, B₂O₃, MgO, CaO, and SrO,and the other of which (Glass B) contained seven component, i.e., thesame six as Glass 1 plus BaO. Both glasses were suitable for displayapplications, with Glass B having a higher strain point than Glass A.

The parameters used to model the non-equilibrium viscosity of theglasses are set forth in Table 1. Glass A was used as the referenceglass and thus the parameters which are a function of x_(ref) are forthis glass. As noted above, T_(g)(x) and m(x) are measured values forthe two glasses.

The results for Glass A are shown in FIGS. 1-2 and those for Glass B inFIGS. 3-4. The curves in these figures are labeled by the temperature ofthe experiment (in degrees Celsius). All the experiments shown here wereconducted under isothermal conditions.

In particular, FIG. 1 shows optimized model deflection curves for GlassA and FIG. 2 shows the corresponding viscosity curves. The solid curvesare measured data from the beam bending experiments, and the dashedcurves are model predictions obtained using the composition-dependentnon-equilibrium viscosity model disclosed herein. The numbers next tothe various curves are the temperatures in ° C. at which the beam washeld during the experiments or assumed to be held during the modeling.The ability of the model to accurately predict/estimate glass dynamicsis evident from these figures.

FIGS. 3 and 4 follow the same format as FIGS. 1 and 2 for Glass B. Theholding temperatures are higher because Glass B is more heat resistantthan Glass A. As noted above, the Glass B predicted behavior is based onGlass A as a reference glass with no additional fitting parameters.

The modeled viscosity and deflection of Glass B agree well with theexperimental results. When the fictive temperature is much higher thanthe temperature where the beam is kept, the non-equilibrium viscositycomponent will play a more important role than the equilibriumcomponent. This is shown in the beginning part of the deflectionmeasurement. The high accuracy of this part proves the success of thecomposition-dependent non-equilibrium viscosity model. When the fictivetemperature approaches the real temperature at long times, theequilibrium viscosity takes charge of the whole viscosity. The highaccuracy for this part of the viscosity curve is good proof of thecomposition dependent equilibrium viscosity and also the T_(g) and mvalues used in the model.

Example 2

This example illustrates the use of the computer-implemented modeldiscussed above to predict/estimate compaction of a glass article whenthe article is subjected to a post-forming thermal treatment. Arepresentative example of a glass article for which compactionestimation is important is a glass substrate used in the manufacture ofa display, such as, a liquid crystal display (LCD).

Glass substrates are typically produced by forming a glass ribbon frommolten glass and then cutting individual glass sheets from the ribbon,which are subjected to various finishing operations prior to beingprovided to a display manufacturer. The glass ribbon can be produced byvarious techniques including the float and fusion processes. In eachcase, the process begins with molten glass which then goes through acooling process, i.e., a known (given) temperature profile. The profilecan be determined in various ways, a typical technique being to measurethe temperature of the glass as it cools from the molten state using,for example, IR detectors.

FIG. 5 shows a representative temperature profile for a fusion process.In this figure, vertical lines 51 and 52 divide the profile into threeparts, the glass being in equilibrium with the ambient temperature tothe left of line 51, being in transition to a solid state between lines51 and 52 and thus no longer in equilibrium, and in a solid state to theright of line 52. As will be evident, the portion of the temperatureprofile to the right of line 52 includes cooling of the glass down toroom temperature, whereupon it can be finished and shipped to a displaymanufacturer.

As discussed above in connection with Eq. (15), the thermal history ofthe glass shown in FIG. 5 can be expressed by a set of T_(fi)'s obtainedby solving Eq. (15) for the temperature profile that the glass hasexperienced from the time it was in equilibrium, i.e., when it was tothe left of line 51, until it was in a solid state, i.e., when it was tothe right of line 52. This temperature profile is introduced into Eq.(15) through the T variable (temperature variable) which is a functionof time. By determining the T_(fi)'s, the thermal history of the glassprior to any post-forming thermal treatment is captured in a mannerwhich can be subsequently used in the non-equilibrium viscosityequations disclosed above.

For a glass substrate, the post-forming thermal treatment comes about asa result of the formation of electronic components on the substrate. Thespecifics of the thermal treatment will, of course, depend on theelectronic components being produced, but as a general proposition, thethermal treatment includes a number of heating and cooling cycles. FIG.6 shows a representative temperature profile for a typical post-formingthermal treatment used to produce (deposit) thin film transistors on aglass substrate.

To determine the compaction of the substrate due to a temperatureprofile of the type shown in FIG. 6, one begins with the T_(fi)'sdetermined for the temperature profile of FIG. 5. Using the T_(fi)'s,Eqs. (1), (2), (3), (8), and (14) are solved at a series of time points,where the T values in Eqs. (1), (2), and (8) are those of FIG. 6, andthe x, T_(g)(x), m(x), p(x), and S_(∞)(x)/k ln 10 values used in theseequations are those of the glass making up the substrate. For example,these parameters can have values like those set forth in Table 1. Itshould be noted that Eq. (3) implicitly depends on the T values at theseries of time points through its T_(f)variable, which is calculatedusing Eq. (14) at each time point. Eq. (14) implicitly depends on the Tvalues through the solution of Eq. (15) for the T_(fi) values at eachtime point.

The resulting non-equilibrium viscosity versus time values obtained bysolving Eqs. (1), (2), (3), (8), and (14) are then converted intofictive temperatures which, in turn, are converted into compactionvalues at one or more of the time points. In particular, compaction isdefined as a linear strain of the glass at room temperature induced bythe thermal cycle. Compaction (ε) can be calculated as the product ofthe configurational coefficient of thermal expansion (α_(config)) timesthe change in fictive temperature due to the thermal cycle, where byconvention, a negative value of ε indicates shrinkage and a positivevalue indicates expansion:

ε=α_(config)(T _(f)(t ₁)−T _(f)(t ₀))  (18)

where T_(f)(t₀) is the fictive temperature at the beginning of thethermal cycle, e.g., at the end of the temperature profile of FIG. 5,and T_(f)(t₁) is the fictive temperature at the time of interest t₁which often will be the end of the post-forming thermal treatment, e.g.,at time point 61 in FIG. 6.

If the magnitude of the compaction value calculated from Eq. (18) isgreater than desired, the computer-implemented model disclosed hereincan be used to investigate potential changes that will improve thecompaction. For example, the temperature profile of FIG. 5 and/or FIG. 6can be varied and the calculations repeated to determine the directionand magnitude of the resulting predicted/estimated compaction.

Importantly, in addition to changing temperature profiles, thecomputer-implemented model disclosed herein allows for the compositionof the glass to be changed and the calculations repeated with a new setof x, T_(g)(x), m(x), p(x), and S_(∞)(x)/k ln 10 values. As discussedabove, when the composition is changed, Eqs. (5), (7), and (9), andtheir associated equations, can be used to calculate the new T_(g)(x),m(x), p(x), and S_(∞)(x)/k ln 10 values based on fitting parametersobtained for reference glasses having compositions appropriate to theglass being studied for compaction. This is an important advantage ofthe technology disclosed herein since it is often easier to change glasscomposition than to change temperature profiles.

Example 3

This example illustrates the use of the computer-implemented modeldiscussed above to predict/estimate stress relaxation of a glass articlewhen the article is subjected to a post-forming thermal treatment. Arepresentative example of a glass article for which stress relaxation isimportant is a glass substrate used in the manufacture of a portableelectronic device, in particular, a glass substrate used to produce ascratch-resistant touch screen for such a device.

The scratch-resistant properties of such substrates can be produced byion-exchange strengthening of the substrate. The ion-exchange processinvolves submerging the substrate in a molten salt bath at an elevatedtemperature and holding the substrate in the bath at that temperature toallow the ion-exchange process to take place. FIG. 7 shows arepresentative temperature profile for such an ion-exchangestrengthening process. The ion-exchange process produces a compressivestress on the glass which gives the glass its elevated strength.However, the elevated temperature used to achieve ion-exchange allowsthe glass to relax and thus reduce the amount of stress and associatedstrengthening achieved by the ion exchange. Accordingly, the ability topredict/estimate the stress relaxation during ion-exchange allows aglass manufacturer to optimize the strengthening process.

The stress relaxation calculations follow a pattern similar to thatdescribed above in Example 2 for compaction. Thus, the calculationsbegin with a temperature profile for the forming process, e.g., aprofile of the type shown in FIG. 5, and based on that profile, a set ofT_(fi)'s are calculated to represent the thermal history of the glass atthe end of the forming process. Next, as with compaction, thenon-equilibrium viscosity of the glass at a series of time points iscalculated using the temperature profile of the ion-exchange process,e.g., a profile of the type shown in FIG. 7. The non-equilibriumviscosity is then used to set the time scale for the stress relaxationof the glass as it is undergoing the stress enhancement from the ionexchange. Various techniques can be used to calculate the net effect ofthe competition between stress enhancement and stress relaxation, e.g.,a commercial mechanical engineering software package such as that soldby ANSYS (Canonsburg, Pa.) can be used to model the overall processusing the time scale obtained from the computer-implemented modeldisclosed herein.

As with compaction, if the calculated net stress is less than desired,variations can be made in the temperature profiles, such as the profilesof FIGS. 5 and 7, and/or in the composition of the glass. Again, beingable to incorporate the effect of composition on stress relaxation is animportant advantage of the technology disclosed herein. It should benoted that following analogous techniques, stress relaxation duringforming of the glass article can also be predicted/estimated if desired.

Example 4

This example illustrates the use of the computer-implemented modeldiscussed above to predict/estimate thermal sag or thermal creep. Arepresentative example of a glass article for which thermal sag orthermal creep is important is a glass substrate used in the manufactureof a photovoltaic panel. The problem of thermal sag/creep arises becausewhen heated to an elevated temperature, a substrate can acquire a shapewhich becomes locked into (frozen into) the substrate when the substrateis cooled back to room temperature.

Again, the process begins with calculating a set of T_(fi)'s torepresent the thermal history of the glass during formation, e.g., athermal history of the type shown in FIG. 5. As with compaction andion-exchange strengthening, a set of non-equilibrium viscosity valuesare then obtained for the temperature profile which the substrate issubjected to during manufacture of the photovoltaic panel. FIG. 8illustrates a representative profile for such processing. Thenon-equilibrium viscosity values can then be used in, for example, acommercial mechanical engineering software package which, for example,employs a finite-element technique to model spatial behavior and thuspredict the amount of sag/creep that the substrate will undergo. In somecases, the sag/creep can be estimated by using the behavior of a beamcomposed of the glass of interest, in which case an analytical solutionof the type discussed above in connection with Eqs. (16) and (17) can beused.

As with other applications of the computer-implemented model, e.g., thecompaction and ion-exchange strengthening applications discussed abovein Examples 2 and 3, if the sag/creep is greater than desired, the modelcan be used to estimate/predict the effects of temperature profiles(thermal profiles) and/or glass composition on the behavior of thesubstrate during post-forming processing.

From the foregoing, it can be seen that improved techniques forpredicting/estimating the properties of glass materials, specifically, aglass's non-equilibrium viscosity, have been provided. A variety ofmodifications that do not depart from the scope and spirit of theinvention will be evident to persons of ordinary skill in the art fromthis disclosure. The following claims are intended to cover the specificembodiments set forth herein as well as modifications, variations, andequivalents of those embodiments.

TABLE 1 Parameter Units Glass A Glass B log η_(∞) log Pa-s −2.9 −2.9T_(g) (x) ° C. 734.5 794 m (x) — 35.3 36.8 p (x) — 10.88 11.34 A logPa-s 45.19 45.19 ΔH/k ln 10 K 4136.7 4136.7 S_(∞) (x)/k ln 10 — 135.09149.40

What is claimed is:
 1. A method of making a glass article comprising:(I) melting batch materials to produce molten glass; and (II) forming aglass article from the molten glass; wherein: (A) the batch materialscomprise a plurality of viscosity-affecting components which become atleast part of the glass article; and (B) the method is characterized bysaid viscosity-affecting components and/or their concentrations havingbeen selected at least in part using computer-implemented modeling thatpredicted/estimated non-equilibrium viscosity of the molten glass usingan equation where the non-equilibrium viscosity is a function of bothequilibrium and non-equilibrium components, wherein the equilibrium andnon-equilibrium components are each in turn functions of fictivetemperature and composition, and wherein the equilibrium andnon-equilibrium components are each non-zero.
 2. The method of claim 1wherein the non-equilibrium component is additionally a function oftemperature.
 3. The method of claim 2 wherein the equilibrium andnon-equilibrium components are at least part of separate terms in theequation.
 4. The method of claim 3 wherein proportionality of theseparate terms in the equation is a function of glass transitiontemperature of the molten glass.
 5. The method of claim 4 wherein, inthe equation, a logarithm of the non-equilibrium viscosity of the moltenglass is related to logarithms of both the equilibrium andnon-equilibrium components.
 6. The method of claim 5 wherein, in theequation, a decadic logarithm of the non-equilibrium viscosity of themolten glass is related to decadic logarithms of both the equilibriumand non-equilibrium components.
 7. The method of claim 1 wherein thecomputer-implemented modeling predicted/estimated compaction of theglass article during a post-forming thermal treatment.
 8. The method ofclaim 1 wherein the computer-implemented modeling predicted/estimatedstress relaxation of the glass article during forming.
 9. The method ofclaim 1 wherein the computer-implemented modeling predicted/estimatedstress relaxation of the glass article during a post-forming thermaltreatment.
 10. The method of claim 1 wherein the computer-implementedmodeling predicted/estimated thermal sag or thermal creep of the glassarticle during a post-forming thermal treatment.
 11. The method of claim10 wherein the thermal sag or creep was predicted/estimated using thecomputer-implemented modeling in combination with finite-elementmodeling which modeled spatial behavior of the glass article during thepost-forming thermal treatment.
 12. A glass article made by the methodof claim
 1. 13. A system for making a glass article by the method ofclaim 1 comprising a computer and the batch materials.